CN111867819A

CN111867819A - Primer for TAC films and laminates

Info

Publication number: CN111867819A
Application number: CN201980019652.0A
Authority: CN
Inventors: R·贝尔松
Original assignee: Essilor International Compagnie Generale dOptique SA
Current assignee: EssilorLuxottica SA
Priority date: 2018-03-16
Filing date: 2019-03-14
Publication date: 2020-10-30
Anticipated expiration: 2039-03-14
Also published as: AU2019233690B2; EP3539760B1; BR112020018878A2; CN111867819B; AU2019233690A1; US20210011196A1; EP3539760A1; WO2019175354A1

Abstract

Embodiments of the present disclosure relate to primer compositions for increasing adhesion between polarizing film laminates and cast polymerized lenses. The chemisorbed primer may react with the cast polymerized lens monomer and/or interact with the polarizing film laminate to provide exceptionally strong adhesion between the film laminate and the ophthalmic lens.

Description

Primer for TAC films and laminates

Technical Field

The present disclosure relates to the field of ophthalmic lenses, including polarized ophthalmic lenses for eyeglasses and sunglasses.

Background

Many sunglasses include polarizing filters for blocking glare and reducing the overall light transmittance of light passing through the sunglass lenses. Glare effects occur when sunlight is reflected from a flat surface and light is reflected in various directions. The glare perceived by humans is typically reflected horizontal light.

Polarized glasses lens reduce glare by using a filter film in which molecules are aligned parallel to each other. The filter film is typically oriented with the filter molecules aligned vertically. The filter blocks most of the incoming horizontal light while also allowing vertically polarized light to pass through the lens. Since the reflected horizontal light waves cannot bypass the vertical filter, glare is eliminated.

Polarized sunglasses are particularly beneficial to people and fishermen on boats because reflection of light from water can produce intense glare. Polarized sunglasses can also be used for a variety of outdoor activities (including golf, bicycling, driving) and anyone who spends a significant amount of time outdoors because the polarizing lenses block much of the horizontal light reflected from flat outdoor surfaces.

Many polarized lenses are manufactured using a fragile polyvinyl alcohol (PVA) polarizing film having an average thickness of about 30 μm. The polarizing film must undergo several processing steps including thermoforming, shearing to the desired diameter, primer application, and placement into a casting cell. The fragile nature of polarizing films coupled with multiple processing steps increases the likelihood of film damage. Polarizing PVA films are typically laminated between triacetyl cellulose (TAC) films in order to provide a robust protective support layer on the surface of the PVA film.

The interaction of the PVA film laminate with the adhesion primer is critical to the polarized lens production process. Some industrial film primers adversely affect the optical quality of PVA polarizing films and PVA film containing laminates. Some industrial film primers provide poor adhesion properties and cause delamination during one of many lens production and finishing process steps. There is often a trade-off between primer adhesion performance and impact on optical quality.

We are also known from prior art document WO 2018/052454, which describes a reinforced primer formulation. This formulation can be used to enhance adhesion between films or laminates such as triacetyl cellulose (TAC) and polymerizable or polymeric materials in order to reduce or eliminate the possibility of delamination.

Document JP 2016/510131 relates to a UV-curable adhesive composition and a method for producing a polarizing lens by means of said composition, and more specifically to a UV-curable adhesive composition for producing a polarizing lens, said composition comprising 50-80 parts by weight of a monofunctional monomer, 14-49 parts by weight of an oligomer, and 1-6 parts by weight of a photoinitiator.

There is a need in the industry for a polarizing laminate adhesion primer that has minimal impact on optical quality and maintains film adhesion during lens production and finishing process steps.

Disclosure of Invention

Disclosed herein are chemisorbed primers that provide robust adhesion between a functional optical laminate and an ophthalmic article substrate. The primer is formulated to include components that promote adhesion to the functional laminate and/or ophthalmic article substrate. Conventional primers rely on relatively weak primer-to-primer and primer-to-substrate electrostatic forces for adhesion. In contrast, the primers disclosed herein adhere to the surface to which they are applied. The end result of these chemisorbed primers is enhanced adhesion strength and durability.

The primers disclosed herein are particularly useful for adhering TAC-based polarizing laminates in cast CR39 optical elements. The primer is designed to provide a degree of penetration into the surface of the TAC layer or other laminate layer. The film penetration qualities of the primer promote its adhesion characteristics.

In particular, a primer as disclosed herein comprises at least one reactive oligomer or high molecular weight polymer having a Mw between about 2,000 and about 100,000 in an amount ranging from 1 wt.% to 25 wt.%, at least one UV or thermal initiator, and at least one monomer capable of reacting with a lens polymerizing monomer in an amount ranging from 0.25 wt.% to 15 wt.%, wherein the primer coating monomer is the same or different from the lens polymerizing monomer and is selected to include the same reactive functional group as the lens monomer. This primer composition is a curable composition and one skilled in the art will recognize that the curing process will result in chemical reactions that may alter some of the primer components. In some embodiments, the primer component functional groups are selected to interact with the laminate film and react with the substrate to which it will adhere. In this manner, primer compositions as disclosed herein can be designed and tailored to provide adhesion to specific film and/or lens substrate target materials.

In some embodiments, a solvent may be used to dissolve the primer component. When present, the solvent may be included in an amount ranging from 60 wt.% to 98.75 wt.%. In some aspects, the solvent is at least one of a ketone or acetate solvent. Exemplary solvents include, but are not limited to, acetone, methyl ethyl ketone, ethyl acetate, cyclopentanone, and cyclohexanone, and any combination thereof.

According to the present invention, the primer monomer may be the same as the polymerized lens monomer. When the primer monomer is the same as the lens monomer, the monomer helps to compatibilize the primer composition with the lens polymer. According to the present invention, the primer monomer may be different from the lens polymerizing monomer, and in this case is selected to include the same reactive functional group as the lens monomer. In practice, the primer monomer may be different from the lens monomer, but still capable of reacting with the polymerized lens monomer. That is why in this case the primer monomer is chosen to include the same reactive functional groups as the lens monomer. For example, the lens monomer can consist essentially of allyl diglycol carbonate, and the primer monomer can be an allyl ether. Although both the lens monomer and the primer monomer are different compounds, they may react with each other by virtue of their reactive functional groups. In some aspects, the primer monomer comprises a reactive group functionality of 1 or greater, and preferably at least 2. Increasing the reactive functionality increases the types of functional groups with which the primer monomer can react. The primer monomer may include a reactive group or a group selected from the group consisting of: allyl, vinyl, acrylic, thiol, isocyanate, epoxy, and amine.

In some embodiments, at least one reactive oligomer or high molecular weight polymer has a reactive functionality of 1 or greater and preferably 2. Increasing the reactive functionality increases the number or type of functional groups with which the reactive oligomer or high molecular weight polymer can react. In some embodiments, the at least one reactive oligomer or high molecular weight polymer is urethane dimethacrylate (urethane dimethacrylate). In some embodiments, the at least one reactive oligomer or high molecular weight polymer is a methyl methacrylate-based resin.

Some aspects of the present disclosure relate to an optical article according to claim 1. More specifically, some aspects of the present disclosure relate to an optical article comprising an ophthalmic lens made from at least one polymerized monomer, a functional laminate comprising a thermoplastic film on each of a forward-facing surface and a rearward-facing lens-contacting surface, and a primer coating deposited on the lens-contacting surface of the functional laminate. In some embodiments, the functional laminate is a polarizing laminate. The polarizing laminate may include a polyvinyl alcohol (PVA) layer as a polarizing layer. At least one of the functional laminate forward-facing surface thermoplastic film and the rearward-facing lens contacting surface thermoplastic film comprises cellulose Triacetate (TAC). In some embodiments, both the front facing surface thermoplastic film and the rear facing lens contact surface thermoplastic film of the functional laminate are TAC films.

Prior to deposition on the functional laminate, the primer coating comprises an amount ranging from 1 wt.% to 25 wt.%, at least one reactive oligomer or high molecular weight polymer having a Mw between about 2,000 and about 100,000, at least one UV initiator or thermal initiator, at least one monomer capable of reacting with a lens polymerizing monomer in an amount ranging from 0.25 wt.% to 15 wt.%, and optionally a solvent, wherein the primer coating monomer is the same or different from the lens polymerizing monomer and is selected to include the same reactive functional group as the lens monomer. When present, the optional solvent may be included in an amount ranging from 60 wt.% to 98.75 wt.%. In some embodiments, the ophthalmic lens monomer is allyl diglycol carbonate. The primer monomer can react with the ophthalmic lens monomer to provide a chemical bond that forms a strong adhesion base between the functional laminate and the ophthalmic lens. In some aspects, the primer is applied to one or both sides of the functional laminate, dried, UV cured, and then cast in a casting monomer formulation.

In some embodiments, there is provided a method of making a primer coating according to claim 14. More specifically, a method of preparing a primer coating for supporting adhesion between a functional laminate and a contact surface of an ophthalmic lens comprising at least one polymerized monomer is provided. The method comprises the following steps: providing a solvent; and adding to the solvent at least one reactive oligomer or high molecular weight polymer having a Mw between about 2,000 and about 100,000, at least one UV initiator or thermal initiator, and at least one monomer capable of reacting with a lens polymerizing monomer in an amount ranging from 0.25 wt.% to 15 wt.%, wherein a primer coating monomer is the same or different from the lens polymerizing monomer and is selected to include the same reactive functional group as the lens monomer. The solvent is provided in an amount ranging from 60 wt.% to 98.75 wt.%. The primer coating may be fully or partially dried before or after application. A primer coating may be applied on one or both of the functional laminate surface and the ophthalmic lens surface. The primer coating may be provided with an amount of UV light or temperature increase sufficient to activate the initiator and initiate the curing process. The primer may be applied to the TAC polar laminate by flow coating, spin coating, gravure coating, slot die coating, or other means known to those skilled in the art. In some aspects, the primer coating may be dried at a temperature ranging from about 60 ℃ to about 80 ℃ for from about 15 seconds to about 2 minutes. Other drying conditions known to those skilled in the art may be employed to remove the solvent. After drying, the primer can be cured, for example, by using a UV light source. An exemplary, non-limiting source of UV light is Heraeus Noblelight F300S with H + bulbs. The power, energy, and exposure time may be selected to optimize curing. Typical non-limiting curing conditions include about 7 feet per minute (UVA about 1500 mJ/cm) ²About 1200mW/cm²) To about 21 feet per minute (500 mJ/cm)²，1100mW/cm²)。

Any embodiment of any disclosed composition and/or method may consist of or consist essentially of any described element and/or feature and/or step-but not include/contain/have any described element and/or feature and/or step. Thus, in any claim, the term "consisting of …" or "consisting essentially of …" may be substituted for any open-link verb described above, so as to alter the scope of a given claim from what it would otherwise be using the open-link verb.

The term "substantially" and variations thereof are defined as being largely but not necessarily wholly what is specified as understood by one of ordinary skill in the art, and in one non-limiting embodiment substantially refers to a range within 10%, within 5%, within 1%, or within 0.5%.

The terms "about" or "approximately" or "substantially unchanged" are defined as being close to as understood by one of ordinary skill in the art, and in one non-limiting embodiment, the terms are defined to be within 10%, preferably within 5%, more preferably within 1%, and most preferably within 0.5%.

The use of the word "a" or "an" when used in conjunction with the term "comprising" in the claims and/or the specification can mean "one" but also conform to the meaning of "one or more," at least one, "and" one or more than one.

As used in this specification and one or more claims, the word "comprising" (and any form of comprising, such as "comprises" and "comprises"), "having" (and any form of having, such as "has" and "has"), "including" (and any form of including, such as "includes" and "includes)") or "containing" (and any form of containing, such as "containing" and "contains"), is inclusive or open-ended and does not exclude additional, unrecited elements or method steps.

The phrase "and/or" means and or. For purposes of illustration, A, B and/or C includes: a alone, B alone, C alone, a combination of A and B, A and C in combination, B and C in combination, or A, B and C in combination. In other words, "and/or" is used as an inclusive or.

In addition, a device or system configured in a certain way is configured in at least this way, but may be configured in other ways than those specifically described.

The compositions and methods for their use may "comprise," consist essentially of, "or" consist of any of the ingredients or steps disclosed throughout the specification. With respect to the transitional phrase "consisting essentially of," in one non-limiting aspect, the basic and novel features of the compositions and methods disclosed in this specification include the ability of the compositions to reduce or prevent delamination between the film laminate and the cast polymerized lens.

Further aspects of the invention are given in claims 2 to 14. Other objects, features and advantages of the present invention will become apparent from the following detailed description. It should be understood, however, that the detailed description and examples, while indicating specific embodiments of the invention, are given by way of illustration only. In addition, it is contemplated that variations and modifications within the spirit and scope of the invention will become apparent to those skilled in the art from this detailed description.

Detailed Description

Various features and advantageous details are explained more fully with reference to the non-limiting embodiments that are illustrated in the accompanying drawings and detailed in the following description. It should be understood, however, that the detailed description and the specific examples, while indicating embodiments, are given by way of illustration only and not by way of limitation. Various substitutions, modifications, additions and/or rearrangements will become apparent to those of ordinary skill in the art in light of this disclosure.

In the following description, numerous specific details are provided to provide a thorough understanding of the disclosed embodiments. One skilled in the relevant art will recognize, however, that the invention can be practiced without one or more of the specific details, or with other methods, components, materials, and so forth. In other instances, well-known structures, materials, or operations are not shown or described in detail to avoid obscuring aspects of the invention.

Some aspects of the present disclosure relate to a series of primer compositions that have been developed to provide enhanced adhesion between TAC-based polarizing laminates and allyl diglycol carbonate-based ophthalmic lens substrates. The primer is designed to provide a degree of penetration to at least a portion of the surface of the TAC layer or lens substrate. In some embodiments, the inclusion of a solvent or solvent blend helps to allow the primer to penetrate the TAC layer or lens substrate surface. The penetration of the primer is to anchor the primer to the TAC-based laminate and/or the ophthalmic lens substrate and to supplement adhesion. When used in conjunction with a lens casting process, a primer is applied to the TAC polarizing laminate, optionally dried, optionally cured, and then cast in a cast monomer formulation.

Example 1

UV reactive solid acrylic beads based on methyl methacrylate and tripropylene glycol diacrylate having a Mw of 32,500, an acid value of 0.0, a Tg of 75 ℃ (reactive high molecular weight polymer,

4026, celluloid International (Lucite International) weighed into glass vials. Ethyl acetate was added and mixed until the polymer dissolved. The addition of allyl diglycol carbonate (monomer,

PPG Co.) and UV initiator: (

819 BASF) and stirred until dissolved. The amounts and ratios are provided in table 1 below.

Table 1: primer formulation, example 1

Components	Wt.(g)	Wt.％
			Polymer and method of making same	1.0	10.0
Solvent(s)	8.7	87.0
			Monomer	0.2	2.0
UV initiator	0.1	1.0

Example 2

The solvent, monomers and UV initiator of example 1 were retained and the polymer based on methyl methacrylate, n-butyl methacrylate and tripropylene glycol diacrylate (reactive high molecular weight polymer,

4059 celluloid international corporation) instead of the reactive high molecular weight polymer. The amounts and ratios of the components remained the same as in example 1.

Example 3

Retaining the solvents, monomers and UV initiator of example 1, with an aliphatic polyester-based urethane dimethacrylate oligomer having a Tg of 78 (R) ((R))

CN1963) instead of the reactive high molecular weightA compound (I) is provided. The amounts and ratios of the components remained the same as in example 1.

Example 4

Retaining the solvent, monomers and UV initiator from example 1, with a low molecular weight urethane dimethacrylate oligomer having a Tg of 189 ℃ ((

CN1964) instead of a reactive high molecular weight polymer. The amounts and ratios of the components remained the same as in example 1.

Lens casting and layering: primer examples 1-4

The TAC/PVA/TAC polarizing laminate wafers were coated separately with the primers of examples 1-4, dried and exposed to UV radiation. These wafers were cast separately on allyl diglycol carbonate (lens monomer,

PPG company) and the resulting lenses were subjected to a surface and aggressive edging test (SET) and checked for delamination. Table 2 depicts the delamination test results for primer examples 1-4.

Table 2: primer examples 1-4, SET adhesion results

	Example 1	Example 2	Example 3	Example 4
					4-basic lens	2/2 through	Not applicable to	2/2 through	6/6 through
5-basic lens	3/4 through	3/6 through	4/4 through	Not applicable to
					SET adhesion	Good effect	In general	Good effect	Good effect

Lens casting and layering: comparative example

A control was performed using a non-reactive polyurethane terminated with hydroxyl groups in Methyl Ethyl Ketone (MEK) and ethyl acetate. Allyl diglycol carbonate monomer is included in amounts of 0%, 0.4% and 0.8%. The primer was applied on a TAC polarized wafer and cast separately in allyl diglycol carbonate. For the control primer, no adhesion was obtained.

Table 3: comparative example, SET adhesion results

The presently disclosed chemisorbed primer compositions provide enhanced adhesion between the TAC laminate and cast allyl diglycol carbonate lenses. The claims should not be construed to include device-plus-function or step-plus-function limitations unless such limitations are expressly recited in a given claim using one or more of the phrases "device for …" or "step for …," respectively.

Claims

1. An optical article, comprising:

an ophthalmic lens comprising at least one polymerized monomer,

a functional laminate comprising a thermoplastic film on each of a forward-facing surface and a rearward-facing lens-contacting surface,

a primer coating deposited on the lens contacting surface of the functional laminate,

wherein on the functional laminate, the primer coating comprises:

at least one reactive oligomer or high molecular weight polymer having a Mw between about 2,000 and about 100,000 in an amount ranging from 1 wt.% to 25 wt.%;

at least one UV initiator or thermal initiator; and

at least one monomer capable of reacting with the lens polymerizing monomer, wherein the monomer is present in an amount ranging from 0.25 wt.% to 15 wt.%, wherein the primer coating monomer is the same or different from the lens polymerizing monomer and is selected to include the same reactive functional group as the lens monomer.

2. The optical article of claim 1, wherein the primer coating comprises a solvent in an amount ranging from 60 wt.% to 98.75 wt.%.

3. The optical article of claim 1, wherein the at least one reactive oligomer or high molecular weight polymer has a reactive functionality of 1 or greater and preferably 2.

4. The optical article of claim 1, wherein the at least one reactive oligomer or high molecular weight polymer is urethane dimethacrylate.

5. The optical article of claim 1, wherein the at least one reactive oligomer or high molecular weight polymer is a methyl methacrylate-based resin.

6. The optical article of claim 1, wherein the primer coating monomer comprises a reactive group selected from the group consisting of: allyl, vinyl, acrylic, thiol, isocyanate, epoxy, and amine.

7. The optical article of claim 1, wherein the primer coating monomer comprises a reactive group functionality of 1 or greater, and preferably at least 2.

8. The optical article of claim 2, wherein the solvent is at least one of a ketone solvent or an acetate solvent.

9. The optical article of claim 8, wherein the solvent is selected from the group consisting of: acetone, methyl ethyl ketone, ethyl acetate, cyclopentanone, and cyclohexanone, or any combination thereof.

10. The optical article of claim 8, wherein the solvent is ethyl acetate.

11. The optical article of claim 1, wherein the functional laminate is a polarizing laminate.

12. The optical article of claim 11, wherein the polarizing laminate comprises a polyvinyl alcohol (PVA) polarizing layer.

13. The optical article of claim 1, wherein at least one of the functional laminate forward-facing surface thermoplastic film and the rearward-facing lens contacting surface thermoplastic film comprises cellulose Triacetate (TAC).

14. A method of preparing a primer coating for supporting adhesion between a functional laminate and a contact surface of an ophthalmic lens comprising at least one polymerized monomer, the method comprising:

providing a solvent; and adding

At least one reactive oligomer or high molecular weight polymer having a Mw between about 2,000 and about 100,000 in an amount ranging from 1 wt.% to 25 wt.%,

at least one UV initiator or thermal initiator, and

At least one monomer capable of reacting with the lens polymerizing monomer, wherein the monomer is present in an amount ranging from 0.25 wt.% to 15 wt.%, wherein the primer coating monomer is the same or different from the lens polymerizing monomer and is selected to include the same reactive functional group as the lens monomer,

wherein the solvent is provided in an amount ranging from 60 wt.% to 98.75 wt.%; and

providing UV light or a temperature increase in an amount sufficient to activate the initiator.